Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B29/00—Monoazo dyes prepared by diazotising and coupling
  • C09B29/10—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group
  • C09B29/12—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group of the benzene series
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B29/00—Monoazo dyes prepared by diazotising and coupling
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B29/00—Monoazo dyes prepared by diazotising and coupling
  • C09B29/24—Monoazo dyes prepared by diazotising and coupling from coupling components containing both hydroxyl and amino directing groups
  • C09B29/26—Amino phenols
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
  • C09B31/02—Disazo dyes
  • C09B31/06—Disazo dyes from a coupling component "C" containing a directive hydroxyl group
  • C09B31/062—Phenols
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/003—Marking, e.g. coloration by addition of pigments
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/226—Organic compounds containing nitrogen containing at least one nitrogen-to-nitrogen bond, e.g. azo compounds, azides, hydrazines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
  • C10M171/007—Coloured or dyes-containing lubricant compositions
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
  • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
  • G01N33/26—Oils; Viscous liquids; Paints; Inks
  • G01N33/28—Oils, i.e. hydrocarbon liquids
  • G01N33/2835—Specific substances contained in the oils or fuels
  • G01N33/2882—Markers

Definitions

• the present invention relates to a new method for the detection of mineral oils marked with azo dyes, the use of mono- or disazo dyes as marking agents for mineral oils and new azo dyes.
• US-A-3 764 273 describes the extraction of quinizarine derivatives and of special azo dyes and the like. with aqueous alkali and dimethyl sulfoxide.
• X 1 is hydrogen, C 1 -C 4 -alkyl, cyano, nitro or phenylazo, which is optionally mono- or disubstituted by C 1 -C 4 -alkyl,
• X 2 is hydrogen, C 1 -C alkyl, cyano, nitro, C 1 -C alkoxy or C 1 -C 6 alkoxycarbonyl,
• X 3 is hydrogen, -CC 4 -alkyl, cyano or Ci-Ci ⁇ , -alkoxycarbonyl and
• X 4 is hydrogen, hydroxy, Ci-Cs-alkyl, which is optionally substituted by phenyl, -CC alkoxy, amino, -CC 4 -dialkylamino or -C-Ci 6 monoalkylamino, the al yl chain of which, if appropriate, by 1 to 3 oxygen atoms are interrupted in ether function, mean
• an organic solvent which is partially or completely miscible with water and as a base an alkali or alkaline earth metal hydroxide, an alkali carbonate or an ammonium compound of the formula II
• R 1 , R 2 , R 3 and R 4 are each independently of the other -CC 6 -alkyl or benzyl used.
• substituted phenyl or naphthyl groups occur in the above formula I, they may also have different substituents on a phenyl or naphthyl ring at the same time.
• Residues X 1 , X 2 , X 3 , X 4 , R 1 , R 2 , R 3 and R 4 are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.
• X 4 , R 1 , R 2 , R 3 and R 4 are furthermore, for example, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl or isooctyl.
• R 1 , R 2 , R 3 and R 4 are furthermore, for example, nonyl, isononyl,
• Decyl isodecyl, undecyl, dodecyl, tridecyl, 3,5,5,7-tetramethyl-nonyl, isotridecyl, tetradecyl, pentadecyl or hexadecyl (the above names isooctyl, isononyl, isodecyl and isotridecyl are trivial names and derive from those after oxo Synthesis of alcohols obtained - cf. Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 7, pages 215 to 217, and volume 11, pages 435 and 436).
• Residues X 4 are furthermore, for example, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, sec-butylamino, pentylamino, isopentylamino, neopentylamino, 2-pentylamino, tert-pentylamino -Methylpentylamino, heptyl- a ino, octylamino, 2-ethylhexylamino, isooctylamino, nonylamino, isononylamino, decylamino, isodecylamino, undecylamino, dodecylamino, tridecylamino, 3,5,
• Residues X 1 are, for example, phenylazo, 2-, 3- or 4-methylphenylazo or 2,4- or 2,6-dimethylphenylazo.
• Residues X 2 and X 4 are furthermore, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or sec-butoxy.
• Radicals X 2 and X 3 are furthermore, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butox carbonyl, isobutox carbonyl, sec-butoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, tert-pentyloxycarbonyl, hexyloxycarbonyl, 2-methylpentyloxyoxyyl, Octyloxycarbonyl, 2-ethylhexyloxycarbonyl, isooctyloxycarbonyl, nonyloxycarbonyl, isononylox carbonyl, decylox carbonyl, isodecyloxycarbonyl, undecyloxycarbonyl, dodecyloxycarbonyl, tridecyloxycarbonyl, isotridecyloxycarbonyl, tetradecyloxy
• X 2 is hydrogen, -CC alkyl, -CC 4 alkoxy or -C-Ci 6 alkoxy carbonyl and
• X 3 is hydrogen, C1-C 4 -alkyl or Ci-Cig-alkoxycarbonyl and
• Azo dyes of the formula I in which 1 is 1 are preferably used in the process according to the invention.
• Azo dyes of the formula Ia are particularly preferred in the process according to the invention.
• X 1 is hydrogen, cyano, nitro or phenylazo, which is optionally mono- or disubstituted by C 1 -C 4 -alkyl,
• X 2 is hydrogen, -CC 4 alkyl, -C-alkoxy or Ci-Cn-alkoxy carbonyl,
• X 3 is hydrogen or -CC alkyl
• X 4 is hydrogen or -CC 4 alkyl, which is optionally substituted by phenyl. Furthermore, azo dyes of the formula Ib are particularly preferred in the process according to the invention
• X 1 is hydrogen or phenylzo substituted by C 1 -C 4 -alkyl
• X 3 is hydrogen or -CC alkyl
• X 4 is hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -dialkylamino or Ci-Cie-monoalkylamino,
• X 5 is hydrogen or -CC alkyl
• x 6 is hydrogen, -CC alkyl or -CC 4 alkoxy
• Azo dyes of the formula Ia in which X 4 is hydrogen or 1-phenylethyl are very particularly preferably used in the process according to the invention.
• azo dyes of the formula Ia are used in the process according to the invention, in which X 1 is hydrogen or phenylazo which is monosubstituted by methyl, X 2 is methyl or C 1 -C 13 -alkoxycarbonyl and X 3 is hydrogen or methyl.
• Suitable alkali or alkaline earth metal hydroxides or alkali carbonates which can be used in the process according to the invention are, for example, lithium, sodium, potassium, magnesium or calcium hydroxide or lithium, sodium or potassium carbonate.
• Suitable ammonium compounds of formula II are e.g. Tetramethylam onium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide or benzyltributylammonium hydroxide.
• alkali or alkaline earth metal hydroxides as the base is preferred, alkali metal hydroxides being particularly noteworthy.
• lithium, sodium or potassium hydroxide as the base is particularly preferred, sodium hydroxide being of particular importance.
• the alkali metal or alkaline earth metal hydroxides, alkali metal carbonates or ammonium compounds of the formula II are preferably used directly as an aqueous solution, these generally containing alkali metal or alkaline earth metal hydroxide, alkali metal carbonate or ammonium compounds of the formula II 0.1 to 10 wt .-%, preferably 1 to 10 wt .-%, each based on the weight of the aqueous solution.
• Suitable solvents are organic solvents which are partially or completely miscible with water. These are, for example, acid amides, in particular carboxamides, such as formamide, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, pyrrolidin-2-one, l-methylpyrrolidin-2-one (NMP), l, 3-dimethylhexahydropyrimid-2-one or hexamethylphosphonic acid triamide, N, N, N ', N'-tetramethylguanidine, acetonitrile, nitro methane, amines such as 2-aminoethanol, l, 10-diamino-4,7-dioxadecane , l, 13-diamino-4,7,10-trioxatridecane, 2- or 3-methoxypropylamine, 1, 8-bis (dimethylamino) naphthalene
• Preferred solvents are 1-methylpyrazole, pyrrolidin-2-one, l-methylpyrrolidin-2-one, dimethyl sulfoxide or sulfolane.
• the extractant contains further additives, for example 4-nonylphenol, or if 4-nonylphenol is added to the mineral oil before extraction.
• the proportion of solvent is generally 50 to 99% by weight, preferably 90 to 99% by weight.
• Suitable solvents are preferably aromatic hydrocarbons, such as toluene, xylene, dodecylbenzene, diisopropylnaphthalene or a mixture of higher aro aten, which is commercially available under the name Shellsol® AB (Shell).
• Shellsol® AB Shellsol® AB
• cosolvents e.g.
• Alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol or cyclohexanol, glycols, such as butylethylene glycol or methylpropylene glycol, amines, such as triethylamine, diisooctylamine, dicyclo hexylamine, aniline, N-methylaniline, N, N-dimethylaniline, toluidine or xylidine, alkanolamines, such as 3- (2-methoxyethoxy) propylamine, o-cresol, m-cresol, p-cresol, ketones, such as diethyl ketone or cyclohexanone, Lactams, such as ⁇ -butyrolactam, carbonates, such as ethylene carbon
• the azo dye of the formula I passes into the aqueous phase, which is colored in a clearly visible manner.
• Another advantage of the method according to the invention is that dyes which are only slightly acidic can also be extracted.
• Another object of the present invention is the use of azo dyes of the formulas Ia or Ib mentioned above for marking mineral oils.
• Azo dyes of the formula Ia in which X 4 denotes hydrogen or 1-phenylethyl are preferred for marking mineral oils.
• azo dyes of the formula Ia in which X 1 is hydrogen or phenylazo which is monosubstituted by methyl, X 2 is methyl or C 1 -C 13 -alkoxycarbonyl and X 3 is hydrogen or methyl, for marking mineral oils.
• Azo dyes of the formula Ia in which X 1 is phenylazo monosubstituted by methyl, X 2 is methyl and X 3 is hydrogen or methyl are particularly preferably used for marking mineral oils.
• Azo dyes of the formula Ic are also particularly preferred
• YC 7 -Cn alkyl means used for marking mineral oils.
• Mineral oils in the sense of the invention are understood to mean, for example, fuels, such as gasoline, kerosene or diesel oil, or oils, such as heating oil or motor oil.
• the azo dyes of the formula Ia or Ib are particularly suitable for marking mineral oils for which marking is required, e.g. for tax reasons. In order to keep the costs of the marking low, the aim is to use the smallest possible amount of marking agent for the marking.
• Labeling in the sense of the invention means an addition of the azo dyes of the formula Ia or Ib to mineral oils in such a concentration that the mineral oils are either not colored or only slightly visible to the human eye, but the dyes of the formulas Ia and Ib can be easily and clearly detected by the detection methods described in more detail here.
• the azo dyes of the formula Ia or Ib are used either in bulk or in the form of solutions.
• the azo dyes of the formula Ia or Ib to be used according to the invention have the advantage that, depending on their concentration, they are suitable for clearly coloring mineral oils and / or can be used as marking substances.
• azo dyes of the formula Ia or Ib to be used according to the invention it is very easy to detect marked mineral oils, even if the marking substances are only present in a concentration of approximately 10 ppm or less.
• the azo dyes of the formula Ia When used, the azo dyes of the formula Ia have the advantage that they have very good solubility and are also easy to dilute. In addition, they can be used to achieve significantly more bathochromic hues in the detection reaction than with the dyes known from US Pat. No. 5,156,653.
• Another object of the present invention was to provide new azo dyes which are advantageously suitable as marking substances for mineral oils.
• X 1 is hydrogen or phenylzo substituted by C 1 -C 4 -alkyl
• X 3 is hydrogen or -CC 4 alkyl
• X 4 is hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -dialkylamino or C 1 -C 6 -mono- alkylamino,
• X 5 is hydrogen or -CC 4 alkyl
• __- is hydrogen, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy, with the proviso that a) at least one of the three radicals X 1. , X 2 and X 3 is different from hydrogen, b) X 2 also means cyano when X 4 is C 1 -C 4 -dialkylamino, c) X 2 also C 1 -C 4 -alkoxy carbonyl means if all of the radicals X 4 , X 5 and X 6 are different from hydrogen and d) one of the radicals X 1 , X 2 or X 3 also means nitro if X 4 is for Ci- Ci ß -Monoal ylamino and X 6 are -C-C 4 alkyl.
• the new azo dyes of the formula Ib can be obtained by methods which are known per se.
• an aniline of formula III for example, an aniline of formula III
• the further azo dyes of the formula I and those of the formula Ia are generally compounds known per se. They are e.g. in US-A-5 156 653 or US-A-4 473 376 or can be obtained by the methods mentioned therein.
• diesel oil which was marked with the dyes listed below, was detected with various reagent solutions, which are also listed below.
• R5 9.5 parts of amine of the formula H 2 N-CH (CH 3 ) CH 2 [-OCH (CH 3 ) CH 2 ] 2 , 6 -OCH 2 CH (CH 3 ) -NH 2 and 0.5 part of 1 wt .-% aqueous lithium hydroxide solution
• R6 9 parts of 1,3-dimethylhexahydropyrimid-2-one and 1 part
• R9 4 parts dest. Water, 4 parts 1,10-diamino-4,7-dioxadecane and
• color the color of the color of the marker, no substance agent, aqueous phase, oily phase, oily phase, concentrated after shaking in diesel oil before tration
• the dyes F13 and F14 are obtained in an analogous manner.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
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• Pathology (AREA)
• Physics & Mathematics (AREA)
• Analytical Chemistry (AREA)
• Biochemistry (AREA)
• General Health & Medical Sciences (AREA)
• General Physics & Mathematics (AREA)
• Food Science & Technology (AREA)
• Medicinal Chemistry (AREA)
• Biophysics (AREA)
• Molecular Biology (AREA)
• Lubricants (AREA)
• Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
• Paints Or Removers (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Cosmetics (AREA)
• Investigating Or Analysing Materials By Optical Means (AREA)
• Coloring (AREA)
• Spectrometry And Color Measurement (AREA)
• Paper (AREA)
• Plural Heterocyclic Compounds (AREA)
• Lubrication Of Internal Combustion Engines (AREA)
• Analysing Materials By The Use Of Radiation (AREA)
• Developing Agents For Electrophotography (AREA)

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Citations (9)

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• 1993
  • 1993-10-12 DE DE4334678A patent/DE4334678A1/de not_active Withdrawn
• 1994
  • 1994-09-29 PH PH49090A patent/PH32006A/en unknown
  • 1994-09-30 FI FI961602A patent/FI961602L/fi unknown
  • 1994-09-30 BR BR9407810A patent/BR9407810A/pt not_active IP Right Cessation
  • 1994-09-30 JP JP7511234A patent/JPH09504314A/ja active Pending
  • 1994-09-30 HU HU9600946A patent/HU217768B/hu not_active IP Right Cessation
  • 1994-09-30 AT AT94928400T patent/ATE180823T1/de not_active IP Right Cessation
  • 1994-09-30 WO PCT/EP1994/003259 patent/WO1995010581A1/de not_active Ceased
  • 1994-09-30 CN CN94194282A patent/CN1046756C/zh not_active Expired - Fee Related
  • 1994-09-30 DE DE59408367T patent/DE59408367D1/de not_active Expired - Lifetime
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  • 1994-09-30 AU AU77842/94A patent/AU682540B2/en not_active Ceased
  • 1994-09-30 EP EP94928400A patent/EP0723574B1/de not_active Expired - Lifetime
  • 1994-09-30 CA CA002172959A patent/CA2172959A1/en not_active Abandoned
  • 1994-09-30 ES ES94928400T patent/ES2134357T3/es not_active Expired - Lifetime
  • 1994-09-30 DK DK94928400T patent/DK0723574T3/da active
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• 1996
  • 1996-04-11 NO NO961434A patent/NO961434D0/no not_active Application Discontinuation
• 1999
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